CN113549224B - Metal covalent organic framework material with intrinsic white light emission - Google Patents
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Abstract
A metal covalent organic framework material having an intrinsic white light emission. The invention discloses a cage-type Metal Covalent Organic Framework (MCOF) material with intrinsic white light characteristic and high absolute photoluminescence quantum efficiency and application thereof, belonging to the field of material preparation. The molecular formula of the metal covalent organic framework material is { [ (Pb)8Br8)2(FDC)3(s‑2FDC)5]}nThe compound is prepared by taking lead bromide and 2, 5-furandicarboxylic acid as reaction raw materials and adopting a mixed solvent thermal synthesis method. The invention has low preparation cost and simple operation method, the obtained material shows intrinsic broadband white light emission under the irradiation of ultraviolet light at room temperature, the emitted white light has high intensity and stable luminous performance, and the fluorescence intensity and the temperature of the material have certain correlation, and the material can be used as a novel luminescent material for preparing a white light emitting diode or a low-temperature fluorescence thermometer.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to an intrinsic white light broadband emission luminescent material based on a metal covalent organic framework, and a preparation method and application thereof.
Background
White Light Emitting Diodes (WLEDs) are particularly important in solid state lighting technologies and have received much attention because of their potential to significantly reduce energy consumption and greenhouse gas emissions. At present, a commercial white light emitting diode usually adopts a mixed white light generated by coating yellow luminous YAG (yttrium aluminum garnet): Ce fluorescent powder on an InGaN blue light LED lamp, or a mixed white light generated by a near ultraviolet LED lamp mixed with fluorescent powder of three primary colors of red, green and blue. However, the generation of white light by multi-component mixing has the problems of self-absorption, intrinsic color balance, and complex device, so that a single-component intrinsic white material is a main target for realizing WLED.
The invention is based on rigidly conjugated 2, 5-furandicarboxylic acid and lead halide with strong luminescence property, a novel broad-band intrinsic white light emitting cage-type metal covalent organic framework material is obtained by hybridization, the novel broad-band intrinsic white light emitting cage-type metal covalent organic framework material simultaneously has periodically staggered 'organic cage' and 'inorganic cage' structures, intrinsic white light transition is successfully realized based on the interaction of the lead halide in the structures and the 2, 5-furandicarboxylic acid under ultraviolet excitation, the emitted white light intensity is high, the luminescence performance is stable, and the fluorescence intensity and the temperature have certain correlation, so that the novel broad-band intrinsic white light emitting cage-type metal covalent organic framework material can be used as a novel luminescent material. The invention has low synthesis cost, simple preparation method and high yield, the obtained material can show intrinsic broadband white light emission under the irradiation of ultraviolet light at room temperature, the emitted white light has high intensity and stable luminous performance, and the material has certain correlation between fluorescence intensity and temperature, can be used as a novel luminous material and has good application prospect.
Disclosure of Invention
The invention aims to provide a metal covalent organic framework material with intrinsic white light emission and application thereof, the material can realize the intrinsic broadband white light emission with high photoluminescence quantum efficiency, the preparation method is simple, the raw materials are cheap, the yield is high, no harmful product is generated in the preparation process, and the environment-friendly green synthesis is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal covalent organic framework material with intrinsic white light emission has a tetragonal crystal structure, a space group of I4/mmm, and a chemical formula of { [ (Pb)8Br8)2(FDC)3(s-2FDC)5]}nWherein FDC is 2, 5-furandicarboxylic acid (CAS: 3238-40-2), which is a typical tetragonal cage structure with periodically alternating "organic cages" and "inorganic cages". Each asymmetric unit of which contains three lead ions, three bromine atoms and half of five 2, 5-Furandicarboxylates (FDC). Three lead ions in the asymmetric unit adopt eight-atom coordination, except that the number of bromine atoms coordinated with the lead ions is different, and the coordinated dodecahedron form is PbO8-xBrx(x is 2,3, 4). The coordinating atom of the Pb1 ion contains two bromine atoms and six oxygen atoms each from six different FDC carboxyl groups. Interestingly, where the four coordinating oxygen atoms are oxygen atoms shared by four different FDC carboxyl groups after polycondensation, the four condensed FDC ligands form a FDC tetramer by coordination with the Pb ion [ Pb (s-2FDC)2]2-Unit, four [ Pb (s-2FDC)2]2-(Pb) of units connected two by two to form a tetragonal FDC octamer4(s-2FDC)4]Organic cage "
The Pb1 ions are not only the vertices of the square "organic cage" but also the nodes to which the square "inorganic cage" is connected. The tetragonal "inorganic cage" is PbO composed of three Pb ions, oxygen atom and bromine atom coordinated with the Pb ions8-xBrx(x ═ 2,3,4) dodecahedron, and is on the ab plane with the "organic cage" sharing Pb1 ions. The coordinating atom of the Pb2 ion contains three bromine atoms and five oxygen atoms from three different FDC carboxyl groups, respectively. The Pb2 ion and the Pb1 ion belong to the outer layer of the inorganic cage, but are different from the Pb1 ion in that the Pb2 ion not only serves as a connecting node of the organic cage and the inorganic cage on the same plane (ab plane), but also is bridged with an FDC ligand along the c axis, and different planes are connected along the c axis at the junction of the organic cage and the inorganic cage, so that the two-dimensional structure is expanded into a three-dimensional structure. The coordinating atom of the Pb3 ion contains four bromine atoms and four oxygen atoms from two different FDC carboxyl groups, respectively. The inner layer of each "inorganic cage" is formed by eight Pb3 ions and eight bromine atoms in interactive coordination, each Pb3 ion being the respective vertex, and the bromine atom being the center of the edge line of the square cage.
The preparation method of the metal covalent organic framework material is to mix 1.5mmol of PbBr2And 1.5mmol2, 5-furandicarboxylic acid powder is dissolved in 8mL mixed solvent of N, N' -Dimethylacetamide (DMAC) and acetonitrile, then 2.42mmol perchloric acid is added to be mixed and stirred for 30 minutes, then the mixture reacts in a hydrothermal kettle in an oven at 150 ℃ for 3 days, and then the mixture is slowly cooled to room temperature within 2 days to obtain colorless transparent square bulk crystals, namely the metal covalent organic framework material.
The metal covalent organic framework material is applied to the preparation of a White Light Emitting Diode (WLED), and is used as a single-component white light emitting material for preparing a white light emitting diode device by utilizing the characteristics that the luminescent property of the metal covalent organic framework material can generate high-purity intrinsic broadband white light emission when being excited between 290nm and 400nm at room temperature, has high absolute photoluminescence quantum efficiency, can stably work for a long time under the long-term irradiation of air and an ultraviolet lamp and in a solvent, and the like.
The metal covalent organic framework material is applied to the preparation of the low-temperature fluorescence thermometer, the luminous intensity and the temperature of the metal covalent organic framework material have correlation at low temperature, real-time temperature monitoring can be reflected according to different intensities, and the metal covalent organic framework material is used as a fluorescent material for preparing the low-temperature fluorescence thermometer.
The invention has the following remarkable advantages:
(1) the raw materials used in the invention are low-cost lead bromide, 2, 5-furandicarboxylic acid, N' -Dimethylacetamide (DMAC) and acetonitrile which are sold in the market; the method has the advantages of short reaction time, simple operation, high quality of the synthesized single crystal, high purity and high yield, and is suitable for industrial production.
(2) The metal covalent organic framework material can realize high photoluminescence quantum efficiency intrinsic broadband white light emission, the emitted white light has high intensity and stable luminous performance, and the fluorescence intensity of the metal covalent organic framework material has certain correlation with temperature, and the metal covalent organic framework material can be used as a novel luminescent material, so that the metal covalent organic framework material can be used for preparing a white light emitting diode or a low-temperature fluorescence thermometer.
Drawings
FIG. 1 is a crystal structure diagram of the resulting metal covalent organic framework material.
FIG. 2 is a powder X-ray diffraction pattern of the resulting metal covalent organic framework material.
FIG. 3 is an infrared spectrum of the resulting metal covalent organic framework material.
FIG. 4 is a graph of the solid UV-absorption spectrum of the resulting metal covalent organic framework material.
FIG. 5 is a thermogravimetric and differential thermogram of the resulting metal covalent organic framework material.
FIG. 6 is a normal temperature fluorescence emission spectrum of the obtained metal covalent organic framework material, a ligand normal temperature fluorescence emission spectrum thereof, and a corresponding chromaticity CIE coordinate diagram.
FIG. 7 is a fluorescence emission spectrum of the obtained metal covalent organic framework material under excitation of different excitation wavelengths at normal temperature, and a fluorescence emission spectrum and a corresponding chromaticity CIE coordinate diagram under excitation of different wavelengths after continuous irradiation for 15 days under a 365nm ultraviolet lamp.
Fig. 8 is a diagram of a coated white light emitting diode device prepared from the obtained metal covalent organic framework material.
FIG. 9 shows the temperature-variable fluorescence emission spectra (80-300K) of the obtained metal covalent organic framework material and the corresponding CIE chromaticity diagram and the fitting curve of the fluorescence intensity peak value and the temperature.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Examples
1.5mmol of PbBr2And 1.5mmol of 2, 5-furandicarboxylic acid powder in 8mL of a mixed solvent (V) of N, N' -Dimethylacetamide (DMAC) and acetonitrileDMAC:VAcetonitrileTo 3:1), 2.42mmol of perchloric acid were added, mixed and stirred for 30 minutes, then reacted in a hydrothermal kettle in an oven at 150 ℃ for 3 days, and then slowly cooled to room temperature over 2 days to give colorless, transparent tetragonal bulk crystals, which were isolated by suction filtration and washed successively with DMAC and ethanol, and then after drying under vacuum at 60 ℃ for 12 hours, 0.4215g of the target crystals were obtained in 67.5% yield (based on Pb).
Characterization of
1. And (3) crystal structure characterization:
the metal covalent organic framework material adopts an X-ray single crystal diffractometer (SCXRD) to carry out structural characterization on a single crystal sample. The detailed information is as follows: the instrument is a Bruker SMART APEX II type single crystal X-ray diffractometer manufactured by Brucker company. The X-ray source is a Mo target with radiation wavelength
A graphite monochromator. Collecting diffraction points by omega scanning, correcting obtained data by Lp, selecting I>The independent diffraction points of 2 σ (I) were used for single crystal structure analysis. The SCXRD data collected from the crystals were reduced by software APEX3 (including program SAINT), and multi-scan absorption correction was performed by software SADABS (Bruker, version 2016/2), and the single crystal structures were all subjected to double empty-scan absorption correction by software OLEX2 using single crystal structure analysis program SHELXT (version 6.14)The inter-algorithm yields the initial structure, which is then based on F using the structure refinement program SHELXL (version 2018/3)0 2And (3) performing anisotropic refinement on all non-hydrogen atoms in the compound by using a full matrix least square method. The hydrogen atom positions in the compound structure are determined by adopting a geometric hydrogenation method. Mathematical expressions such as a least square function, a deviation factor, a weight deviation factor and a weight factor used in the structural analysis process are as follows:
least squares function:
temperature factor:
deviation factor:
weight deviation factor:
the weight factor is:
the crystal structure analysis shows that the crystal structure of the sample is tetragonal system, the space group is I4/mmm, and the chemical formula is { [ (Pb)8Br8)2(FDC)3(s-2FDC)5]}n. As shown in fig. 1, a typical tetragonal cage structure has periodically alternating "organic cages" and "inorganic cages". Each asymmetric unit of which contains three lead ions, three bromine atoms and half of five 2, 5-Furandicarboxylates (FDC). Three lead ions in the asymmetric unit adopt eight-atom coordination, except that the number of bromine atoms coordinated with the lead ions is different, and the coordinated dodecahedron form is PbO8-xBrx(x is 2,3, 4). The coordinating atom of the Pb1 ion contains two bromine atoms and six atomsOxygen atoms from six different FDC carboxyl groups. Interestingly, where the four coordinating oxygen atoms are oxygen atoms shared by four different FDC carboxyl groups after polycondensation, the four condensed FDC ligands form a FDC tetramer by coordination with the Pb ion [ Pb (s-2FDC)2]2-Unit, four [ Pb (s-2FDC)2]2-(Pb) of units connected two by two to form a tetragonal FDC octamer4(s-2FDC)4]Organic cage "
The Pb1 ions are not only the vertices of the square "organic cage" but also the nodes to which the square "inorganic cage" is connected. The tetragonal "inorganic cage" is PbO composed of three Pb ions, oxygen atom and bromine atom coordinated with the Pb ions8-xBrx(x ═ 2,3,4) dodecahedron, and is on the ab plane with the "organic cage" sharing Pb1 ions. The coordinating atom of the Pb2 ion contains three bromine atoms and five oxygen atoms from three different FDC carboxyl groups, respectively. The Pb2 ion and the Pb1 ion belong to the outer layer of the inorganic cage, but are different from the Pb1 ion in that the Pb2 ion not only serves as a connecting node of the organic cage and the inorganic cage on the same plane (ab plane), but also is bridged with an FDC ligand along the c axis, and different planes are connected along the c axis at the junction of the organic cage and the inorganic cage, so that the two-dimensional structure is expanded into a three-dimensional structure. The coordinating atom of the Pb3 ion contains four bromine atoms and four oxygen atoms from two different FDC carboxyl groups, respectively. The inner layer of each "inorganic cage" is formed by eight Pb3 ions and eight bromine atoms in interactive coordination, each Pb3 ion being the respective vertex, and the bromine atom being the center of the edge line of the square cage. The specific crystallographic data, atomic coordinates and equivalent isotropic displacement parameters, chemical bond lengths and chemical bond angles of the compound are respectively shown in tables 1-4.
TABLE 1 crystallographic data for the crystal structure of the samples
TABLE 2 atomic coordinates of MCOF Crystal Structure (× 10)4) And equivalent isotropic displacement parameter
TABLE 3 chemical bond length of MCOF Crystal Structure
1-X+Y+Z；21/2-Y1/2+X1/2-Z；31/2-Y1/2-X1/2-Z；4+X+Y-Z；5+X,+Y,1-Z；6+Y,+X,+Z；7-Y,-X,+Z
TABLE 4 chemical bond angles (°) of the MCOF crystal structure
Producing a symmetric transformation of equivalent atoms:1-x,+y,+z；21/2-y,1/2+x,1/2-z；31/2-y,1/2-x,1/2-z；4-1/2+y,1/2-x,1/2-z；5+x,+y,-z；6+x,+y,1-z；7+y,+x,+z；8-y,-x,+z；9+x,1-y,+z
2. powder diffraction characterization:
powder X-ray diffraction (PXRD) data of the compounds were performed on a Rigaku Ultima type IV powder diffractometer with Cu target Ka radiation
The operating voltage is 40kV/mA, the scanning speed is set to be 5sec/step, the scanning step is 0.02 DEG, and the 2 theta angle range of the scanning angle is 5-50 deg. The data after the test is refined by using software PDXL2 (science). The compound simulation standard cards in the PXRD spectrogram are calculated by using single crystal data CIF files by using software Mecury and FullProf. As shown in fig. 2, PXRD test for stability of compound in solvent by continuous irradiation under ultraviolet ray, and temperature resistance test in air. After the compound is soaked in an organic solvent (ethanol, acetonitrile, DMF, DMAC, DMSO, dichloromethane and the like) for 1 day and a DMAC solution with the pH value of 13 is soaked for 1 day, the peak shapes of the peaks in the PXRD spectrogram can still be well corresponded, and the compound is proved to have excellent solvent stability. Meanwhile, after the compound is respectively placed under a 365nm ultraviolet lamp for continuous irradiation for 15 days and is kept stand in air at 100 ℃ for 1 day, the peak shapes of all peak positions in PXRD spectrograms of the compound can still be well corresponded, and the compound is proved to have good light stability.
3. And (3) infrared spectrum characterization:
infrared Spectroscopy (IR) data of the compounds obtained on a Thermo Scientific Nicolet Is50 FT-IR spectrometer. Testing parameters: the instrument adopts an ATR mode, the scanning frequency is set to be 32, and the wave number scanning range is 4000-400cm-1. Before testing, appropriate crystals of the compound were selected, ground to a powder and then testedAnd (6) carrying out testing. The infrared absorption peaks and the assignments of the infrared absorption peaks of the compounds are shown in Table 5. The results are shown in FIG. 3, the compounds are shown in
There is a strong stretching vibration peak of the ester group, which proves that the dehydration polycondensation of the carboxyl group into the ester group coordination is really present in the structure. In addition, the
A series of characteristic peaks are assigned as the expansion vibration peaks of Pb-O bonds.
Main infrared characteristic peak and attribution of compounds in Table 5
4. Solid uv-vis absorption characterization:
solid ultraviolet-visible diffuse reflectance spectroscopy (UV-DRS) data for the compounds were obtained from UV-2600 UV spectrophotometer, Shimadzu corporation, Japan. The instrument parameters are as follows: integrating sphere, BaSO of high purity during testing4As a reference, the scanning wavelength range was set at 200-800nm with a scanning step of 1 nm/sec. And calculating the optical absorption edge and the band gap corresponding to the compound according to the tested UV-DRS spectrogram by adopting a Kubelka-Munk function. The Kubelka-Munk function transformation formula is as follows, where α is the absorption coefficient, s is the scattering coefficient, and R is the reflectivity.
The solid UV-visible absorption spectrum of the compound is shown in FIG. 4, and its broad and strong absorption band in the UV region (peak positions near 211 and 253 nm) can be attributed to n → π or π → π transitions due to five-membered rings on the FDC ligands. And in the visible region, its absorption intensity is negligible. The ultraviolet-visible absorption spectrum intensity of the compound in the ultraviolet region is much higher than that in the visible region, probably due to the larger pi-conjugated system of FDC. Moreover, the absorption band edge of the compound is only 346nm, and the optical band gap of the compound is about 3.78eV according to an optical band gap diagram converted by a Kubelka-Munk function.
5. Thermal stability and differential thermal analysis characterization:
thermogravimetric (TGA) data in the compounds were obtained in a TGA/DSC 3+ simultaneous differential thermogravimetric analysis test by mettler-toledo. The instrument parameters are as follows: the test sample mass is 5.0000-12.0000 mg, the protective gas in the test process is argon, the test temperature range is 30-800 ℃, and the heating rate is 10 ℃/min. As shown in fig. 5, when the temperature reached 203 ℃, the compound began to melt into a liquid and then began to decompose in a first stage around 220 ℃, with a weight loss ratio of about 33%, this stage being mainly the decomposition of the organic ligands in the "organic cages". When the temperature reaches 301 ℃, the compound starts to decompose in a second stage, the compound just starts to slowly lose weight in the stage, and when the temperature exceeds 500 ℃, the weight loss proportion is sharply increased. The inorganic cage is mainly decomposed in the stage, the slow weight loss at the beginning is probably because the Pb-Br bond fracture needs higher energy, and when the experiment reaches a certain temperature and meets the decomposition temperature, the whole molecule is subjected to rapid weight loss.
6. Characterization of luminescence properties:
steady state fluorescence spectroscopy (PL) data for the compounds were obtained by testing on an FLS980 model steady state/transient fluorescence spectrometer from edinburgh, uk. The instrument parameters are as follows: the Xe lamp is used as a light source, the photomultiplier is used as a detector, the scanning wavelength is set to be 290-800 nm, the scanning step length is 1nm, the response time is 0.1-0.3 second, the scanning times are 1-3 times, and the slit of the instrument is self-adaptive according to the intensity of light emitted by a sample. Steady state fluorescence spectroscopy data for different excitation wavelengths of the compounds were also obtained from tests on an FLS980 model steady state/transient fluorescence spectrometer from edinburgh, uk. The difference is only that the set wavelength of the excited sample is different, the parameters of the rest instruments are consistent, and the sample position is not changed when PL spectra of the same compound with different wavelengths are tested. The effect of temperature on luminescence can be explored by testing successive PL spectra at different temperatures. Steady state fluorescence spectra data for the compounds at different temperatures were also obtained from testing on an FLS980 model steady state/transient fluorescence spectrometer from edinburgh, uk. Before testing, the sample chamber of the instrument was replaced with a cryostat attached system from oxford, england and the outer vacuum layer of the system was evacuated. After the sample is packaged, the air tightness of the system is checked, and the internal sample bin of the system is vacuumized (the former is maintained for about 15-20 hours, and the latter is maintained for about 30-60 minutes, and the degree of vacuumizing directly influences the constant temperature effect of the sample). The testing temperature range is 77K-443K, the cooling medium is liquid nitrogen, and the other testing parameters are consistent with the normal temperature testing.
The emission spectrum of the compound measured at room temperature and the solid ultraviolet spectrum thereof are shown in fig. 6, and the corresponding photophysical properties thereof are summarized in table 6. Under the excitation of ultraviolet light of 4W 365nm, the compound shows wide bluish white light emission (the peak value of a fluorescence spectrum is 501nm), the corresponding fluorescence spectrum covers most of a visible light region and a near infrared light region, and the corresponding CIE chromaticity coordinates are (0.3109, 0.3716). This is close to the CIE chromaticity coordinates (0.3333 ) of pure white light. Accordingly, its color temperature (CCT) is 6337K, somewhat approaching the range of "cool white", which is close to the color of light in shadow on a sunny day. In contrast to the ambient fluorescence emission spectra of pure 2, 5-furandicarboxylic acid (FDCA), we have respectively at 368nm (. lamda.)ex320nm) and 418nm (λ)ex350nm) a narrower (violet) and slightly broader (red) fluorescence emission band is observed, which may be due to the fluorescence of FDCA due to its pi → pi transition at different excitation wavelengths. Therefore, from the fluorescence emission spectrum of pure FDCA, it can be concluded that the fluorescence emission peak of the compound near 501nm is caused by the red shift phenomenon caused by pi → pi transition caused by perturbation of FDCA from 418nm by the Pb center. This corresponds to Pb on excitation2+6s of luminescent center2The movement of the lone pair is related. Pb2+The coordination of the luminescence center and the FDC causes the fluorescence emission spectrum of the compound to generate larger Stokes shift (245nm,2.3eV), which leads the original FDCA to emit in the blue light regionThe emission peak gradually red-shifted to the bluish-white light region. In addition, the absolute photoluminescence quantum yield of the compound is as high as 23.7%.
Photophysical properties of the compounds of Table 6
Note: lambda [ alpha ]exRepresents the excitation wavelength; lambda [ alpha ]emRepresenting the emission peak position; CIE denotes chromaticity coordinates; CCT represents a color temperature; tau isavRepresents the fluorescence lifetime having an excitation wavelength of 405nm and an emission wavelength of 501 nm; Φ represents the absolute photoluminescence quantum yield.
As shown in fig. 7, other test conditions were unchanged, only the excitation wavelength was changed, and the fluorescence emission spectra of the test compounds at different excitation wavelengths were measured. The fluorescence emission intensity of the compound is increased with the increase of the excitation wavelength, the full width at half maximum (FWHM) is gradually narrowed with the increase of the fluorescence emission peak intensity, and the corresponding peak position is blue-shifted from 564nm (lambda)ex290nm) gradually blue shifted to 486nm (λ)ex390 nm). The FWHM becomes narrower, and the peak shape of the fluorescence emission spectrum of the compound also tends to the peak shape of the fluorescence emission spectrum of the ligand FDC, and the fluorescence color is changed from yellow-white light region (lambda)ex290nm) gradually moves to a blue-white light region (λ)ex390 nm). This indicates that as the excitation wavelength increases, the fluorescence emission of the compound gradually changes to be dominated by the pi → pi or n → pi electron transition of the ligand FDC, which is generated by the interaction of the original metal Pb ion with the ligand FDC. When the compound is continuously irradiated under an ultraviolet lamp of 4W 365nm for 15 days, the crystal appearance and the fluorescence spectrum of the compound are slightly changed. The PXRD experiment shows that the peak intensity and the peak position of the PXRD spectrogram do not change obviously, which indicates that the compound still exists stably, and the reason for the change is probably that the bond length and the bond angle of the compound change slightly but not obviously under the long-time irradiation of an ultraviolet lamp. This is also confirmed by the X-ray single crystal diffraction test, which gives cell parameters consistent with the original cell parameters. On the basis of this, we measured itFluorescence emission spectra of different excitation wavelengths were tried. The fluorescence emission intensity of the compound also increased with increasing excitation wavelength, except that its FWHM did not change significantly, with a slight red shift at the peak position followed by a blue shift to 530nm (λ)ex400nm), the fluorescence color is determined by yellow-white light region (lambda)ex310nm) slowly moving towards a pure white light area. This is probably because the bond length and bond angle of the compound slightly change with long-term ultraviolet irradiation, and its Pb-Br bond becomes active, so that the electron transition of the lead bromide center is enhanced, and at the same time, the electron transition is based on s2-metal-centered complex of Pb2+The lone electron pair effect in the compound is relative to the FDC, and the fluorescence emission peak can generate larger Stokes shift, and under the combined action of pi → pi or n → pi electron transition of the ligand FDC and the enhanced transition of the Pb ion center, the fluorescence emission of different excitation wavelengths of the compound is converted. When the compound is prepared into a coating type white light emitting diode, as shown in fig. 8, it successfully realizes device light emission.
As shown in fig. 9, other test conditions were unchanged, only the sample temperature was changed, and the fluorescence emission spectra (80 to 300K) of the test compounds at different temperatures were varied. The excitation of the compound at 350nm at room temperature showed a peak at 505nm and the sample showed yellowish white light. When the temperature was decreased from 300K to 80K, the peak intensity at 505nm gradually increased and the peak position gradually red shifted to 513 nm. In addition, when the sample was cooled to 240K, a new emission peak appeared at 500nm and gradually blue shifted to 492nm with decreasing temperature and the peak intensity gradually exceeded the original emission peak at 505 nm. The yellow-white light emission of the compound is derived from Pb2+Large Stokes shift of luminescence centers (245nm,2.3eV), which is comparable to 6s upon excitation2The movement of the lone pair is related. The intensity of the temperature-variable fluorescence curve gradually increased as the sample temperature gradually decreased from 300K to 80K, but the full width at half maximum (FWHM) gradually decreased from 0.71eV (300K) to 0.43eV (80K). The yellow-white emission of the compound gradually changed to a greenish emission. The reasons for this change can be roughly summarized as: due to strong electron-phonon coupling in the compound, under the illumination of different specific excitation wavelengthsA Free Exciton (FE) can relax into a self-trapped exciton (STE) in a frame that is distorted by deformation. However, under low temperature conditions, insufficient thermal energy makes it difficult to de-trap carriers from the STE state to the FE state, which results in an increase in broadband light emission intensity. In addition, quenching of fluorescence emission intensity with increasing temperature is also associated with thermal activation of non-radiative decay pathways. Fluorescent probes are one of the potential applications for highly efficient luminescent materials. The compound has a certain relation between the fluorescence intensity peak value and the temperature in a variable temperature fluorescence emission spectrum from 300K to 80K:
where I is the relevant fluorescence intensity and T is the absolute temperature (in K). The degree of fitting correlation reaches R2The result is that the compound is a potential fluorescence thermometer which is sensitive and accurate at 80-300K as 0.9974.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. A metal covalent organic framework material having intrinsic white light emission, characterized by: the crystal structure is tetragonal system, and the space group is I4/mmmThe chemical formula is { [ (Pb)8Br8)2(FDC)3(s-2FDC)5]}nN = 1/2; wherein FDC is 2, 5-furandicarboxylic acid, and s-2FDC represents the dehydrating polycondensation of two 2, 5-furandicarboxylic acids to form one (s-2FDC)2-A molecule; the structure is a typical square cage structure, and is provided with periodically staggered 'organic cages' and 'inorganic cages'; each asymmetric unit of which contains three lead ions, three bromine atoms and one half of five 2, 5-furandicarboxylic acid salts; three lead ions in the asymmetric unit adopt eight-atom coordination, except that the number of bromine atoms coordinated with the lead ions is different, and the coordinated dodecahedron form is PbO8-xBrxX =2, 3, 4; the coordinating atom of the Pb1 ion contains two bromine atoms and six atoms each derived from six different FOxygen atom of DC carboxyl group; wherein the four coordinating oxygen atoms are oxygen atoms common to four different FDC carboxyl groups after polycondensation, the four condensed FDC ligands forming a FDC tetramer by coordination with Pb ions [ Pb (s-2FDC)2]2-Unit, four [ Pb (s-2FDC)2]2-(Pb) of units connected two by two to form a tetragonal FDC octamer4(s-2FDC)4]"organic cage"; pb1 ions are not only the vertexes of the square "organic cage", but also the nodes connected by the square "inorganic cage"; the tetragonal "inorganic cage" is PbO composed of three Pb ions, oxygen atom and bromine atom coordinated with the Pb ions8-xBrxX =2, 3,4 dodecahedron construction and is on the ab plane with the "organic cage" sharing Pb1 ions; the coordinating atom of the Pb2 ion contains three bromine atoms and five oxygen atoms from three different FDC carboxyl groups, respectively; pb2 ion and Pb1 ion belong to the outer layer of the inorganic cage, but are different from Pb1 ion, Pb2 ion not only is used as the connection node of the organic cage and the inorganic cage of the same plane, namely ab face, but also is bridged with an FDC ligand along the c axis, and different planes are connected along the c axis at the juncture of the organic cage and the inorganic cage, so that the two-dimensional structure is expanded into a three-dimensional structure; the coordinating atom of the Pb3 ion comprises four bromine atoms and four oxygen atoms from two different FDC carboxyl groups, respectively; the inner layer of each "inorganic cage" is formed by eight Pb3 ions and eight bromine atoms in interactive coordination, each Pb3 ion being the respective vertex, and the bromine atom being the center of the edge line of the square cage.
2. A method of preparing the metal covalent organic framework material of claim 1, characterized in that: 1.5mmol PbBr2And 1.5mmol of 2, 5-furandicarboxylic acid in 8mL of a mixed solvent of N, N' -dimethylacetamide and acetonitrile, and 2.42mmol of perchloric acid was added thereto and stirred for 30 minutes at 150 degrees°C, reacting at constant temperature for 3 days, and slowly cooling to room temperature within 2 days to obtain the metal covalent organic framework material.
3. Use of a metal covalent-organic framework material according to claim 1, characterized in that: the metal covalent organic framework material is used for preparing a white light-emitting diode or a low-temperature fluorescence thermometer.
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